Method and apparatus for synthesizing nitrogen compounds



Dec; 15, 1936. HERRMANN 2,064,260

METHOD AND APPARATUS FOR SYNTHESIZING NITROGEN COMPOUNDS Filed March '7,1951 to be a vacuum-tube which permits the exit of Patented .Dec. 15,1936 UNITED STATES,

METHOD APPARATUS FOR SYNTHESIZ- I ING NITROGEN COMPOUNDS LudwigHerrmann, Frankfort-on-the-Main, Ger- -many, assignor to Kurt Adamczickand Willy List, both 0! Frankfort-on-the-Main, Germany Application MarchI, 1931, Serial No. 520,923

In Germany March 8, 1930 I 23 Claims.

duction of certain nitrogen compounds and means serving therefor.

In making my experiments I started from the so-called Lenard-tube. ALenard-tube is known theelectrons or cathode-rays produced therein. Forthis purpose the vacuum-tube or vessel is provided with a windowconsisting of a thin metahfoil. Such tubes or vessels had been alreadyused for influencing chemical reactions by the electrons or cathode-raysemitted therefrom.

In such a vacuum-tube X-rays also are produced in larger or smallerquantities.

My invention is based upon the observation that new and unexpectedeffects are produced if the tube is so constructed that positive raysalso strike against its window. Positive rays are understood to be boththe canal-rays or diacathode-rays discovered by Goldstein and theanode-rays discovered by Gehrcke and Reichenheim. I have ascertained theunexpected fact that the efiects I had observed are not produced if twovacuum-tubes are joined to a common reaction chamber, one of which tubesemits only cathode-rays through its window into the reaction chamberwhereas in the other tube only canal-rays are directed against thewindow separating the last mentioned tube from the reaction chamber. Itis on the contrary necessary for obtaining the effects characterizing myinvention to produce in the same vacuum-tube or bulb both thecathode-rays and the positive rays and to direct them both against awindow provided at the tube.

In the accompanying drawing some embodiments of apparatus constructedaccording to my invention are, illustrated which I used in carry ing outchemical syntheses.

Figure 1 is a plan view of one embodiment partly in section.

Figure 2 is a section on line A-B of Fig. 1.

Figure 3 shows schematically a reactionchamber for the production ofammonia sulphate.

Figure 4 shows a further embodiment of an apparatus for the productionof positive and negative rays, partly in section.

Figure 5 shows a side elevation of the apparatus according to Fig. 4partly in section.

As illustrated in Figures 1 and 2 the tube I is provided with fivetubular extensions 2a, -2b, 3, 4 and 5 for introducing electrodes. Inthe upper extension 4 the leading-in conductor for the cathode 6 isarranged. The cathode 6 has a pocket 6a in which a heating-coil forheating the cathode is inserted. A circular cathodedisc id is fixed byan arm 6c to the cathodebody 6. This disc forms the cathode for the aanode I or target serving for the production of X-rays and shaped insuch a manner as the anticathodes or targets of X-ray tubes for medicalpurposes. The bushing of the anode 1 passes the tubular extension 5; Theanode l is cooled by w the cooling-coil 8. In the oblique tubular extension 3 is arranged the leading-in conductor 9a of a second cathode 9which is a piercedcathode. This has a large aperture 8b in its centerand small openings towards its pe- 15 riphery. The large aperture 9bserves for letting pass the electrons or cathode-rays emitted by thecathode 6. These electrons are accelerated by the two auxiliaryelectrodes lOa, Illb having a positive potential. The leading- 20 inconductors for these two auxiliary electrodes are arranged in thetubular extensions 2a, 2b. Canal-rays pass through the small openings ofthe pierced electrode 9. The bulb l is provided with a window H which isformed by a thin 25 metal-foil for instance of an aluminium-alloy.Because of the rays passing through the window H excessive heating ofthe window would tend to occur. For preventing this it is cooled by acooling-device with liquid-circuit. The cooling 3o effect of the coil I2is sufllcient for preventing the temperature of the window II fromrising to an unpermissible degree. This window iscovered by a piercedmetal can I 3 cemented to a circular flange of the reaction-chamber 14.This chamber is provided with an inlet pipe I 4a and an outlet pipe Mb.A nozzle I5 is introduced into the reaction-chamber H with its mouth l6opened against the direction of the gas-current and serving for theinjection of o liquids.

The tube I being in operation and air being conducted to thereaction-chamber through the inlet pipe Ha a highly explosive gas isproduced in the reaction-chamber which leaves this cham- 45 her by theoutlet. pipe llb, Preferably water or hydrogen'peroxlde is injectedthrough the nozzle I6.

I have not yet analyzed exactly the chemical combination of the gasproduced by these experimerits. I was able, however, to determine withcertainty that this combination is a compound or a mixture of compoundsof nitrogen. This gas has been found to be an excellent fuel for interunal combustion engines, Before feeding the combustion chamber of theengine with the gas it should be admixed with air.

If the gas produced in the reaction-chamber. It by irradiating air withpositive and negative rays is led according to the Figure 3 into asecond reaction-chamber Il provided with a leading-out pipe Ilo andcontaining ferrous sulphide (res) and water acidifled with sulphuricacid, ammonia sulphate is produced.

' For producing anode-rays in addition to canalrays the anticathode ortarget 'I is provided with a recess fllled with a salt causing thegeneration of anode-rays. Such salts are known to be salts such assodium-, potassiumor'strontium-salts.

I cannot give an explanation of the kind of chemical influence thepositive rays exert, but I presume that the cathode-rays preactivate thegases flowing through the reaction chamber I4 and that the positive raysact as a catalyst. I do not desire to limit the invention-by thistheory. It may be imagined that the rays themselves exercise no directinfluence upon the chemical reaction but produce accompanying secondaryphenomena.

Moreover it is not at all necessary to provide in the tube I a specialanticathode I for producing X-rays. In each vacuum-tubeX-rays areproduced to larger or smaller extent by the cathoderays of the tube.These X-rays are sufllcient for the carrying-out of the synthesesaccording to my invention. In view of this I suppose that X-rays are ofless importance as to the scope of my invention. On the other hand, theaddition of positive rays to the cathode-rays is an essential feature ofmy invention whether the positive rays be merely canalor diacathode-raysor such rays and anode-rays. In making my experiments I have evacuatedthe bulb or vessel I-to an extremely high degree, e. g. to 10- mm. Hg,and for this purpose I leave the pump permanently joined to the bulb.

The bulb I shown in Figures 4 and 5 has two lateral tubular extensions20., 2b provided with re-entrant portions, to which the auxiliaryelectrodes I00, III!) are hermetically sealed. Metal bolts I80, I81)serving as conductors are screwed to the electrodes IIIa, "lb. The upperpart of the glass bulb I has two oblique tubular extensions I9 and 20.An incandescent cathode 2| surrounded by a metal cap 22 is arrangedwithin the upper part of the extension It. An anode 23 with an opening231: for the passage of the electrons or cathode-rays emitted from theincandescent cathode 2I is sealed to a circular re-entrant portion ofthe under part of the tubular extension It. These electrons aredeflected by means of the auxiliary electrodes Illa, ID!) in such amanner that they strike the window II. The extension I 9 carries a smalltubular extension Isa containing the leading-in conductor 23b for theanode 23. An anode 24 is sealed to the re-entrant portion of the tubularextension 20, the lower part of this extension carrying the piercedcathode 25. The openings 25a in this cathode are of small diameter, butthey are many in number. The cathode 25 is put under tension by means ofa leading-in conductor 25b, traversing the small tubular extension 201:of the inclined extension 20. v

A third extension 26 is arranged between the extensions I9 and 20 havinga globular shape and two tubular ends 26a, 26b. The extension 26 iscathode rays emitted from the cathode 2I and accelerated by the field ofthe auxiliary electrodes I0a, lob also the canal or diacathode raysleaving the openings 25a of the pierced cathode 25 are directed againstthis window. The cooling coil cools the window II. A similar coolingdevice may be provided for the target 21. A metal cap I3 is arrangedbelow the window II, said cap having a large number of small openings.The reaction chamber I4 is shaped in. the same manner as the reactionchamber according to the embodiment of the invention shown in Figures 1and 2. It has a leading-in pipe Ila and a leading-out pipe Mb. A nozzleI5 traverses the wall of the reaction chamber I4 the opening of which isdirected against the leading-in pipe Ila, i, e. against the direction ofthe gas current.

Experiments carried out with canal-rays and anode rays only showed nochange of irradiated air or other irradiated substances within thelimits of 10- to 2 l0- mm. Hg and anode tensions between the limits of1.5)(10 to 3.5X10 volts. In all experiments I chose the tensions for theheating of filaments of the cathodes to be about 4 to 6 volts.

In other experiments made under the same conditions I investigated theinfluence of X-rays on atmospheric .air and other substances but I couldnot ascertain any chemical change of the substances irradiated only byX-rays. They had been only ionized by the x-rays.

Further experiments I carried out with cathode rays only, but'with theseexperiments the occurrence of X-rays naturally could not be prevented.They showed a yellow flash up of the irradiated air i. e. its nitrogen,continuing about thirty seconds after irradiation and then disappearing.This phenomenon could be ascertained with a vacuum of 8.3x 10- mm. Hgand a tension of 1.5 (10 volts.

After canal rays and/or anode rays were added to the cathode rays andX-rays the flashing up disappeared and the substances irradiated pro-'duced a chemical compound, the constitution of which I have not yet beenable to determine but which is characterized by a great explosive force.

Although I have referred to the electrodes in the apparatusherein-before described as anode and cathode I wish to state that thishas been done only for the sake of simplicity. In fact some of theelectrodes are entitled to have a multiple function. For avoiding anymisunderstanding I have inserted in the following schedules the voltagesthat might be by way of example applied to the electrodes:

Embodiment according to Figs. 1 and 2 Embodiment according to Figs. 4and 5 Electrode Tension 21,22 0 volt 23 150 volts 24 0 volt 25 200 kv.10m 200 kv. 100 200 kv. 27 200 kv. 28 0 volt common evacuated bulb, andmeans ,for subjecting the said gas to the action of all of said rays.

2. In an apparatus-for carrying out chemical reactions, in combination,a reaction chamber, means for driving gas through this chamber, meansfor producing X-rays, means for producing cathode rays, means forproducing canal rays, all said ray producing means being included in acommon evacuated bulb, and means for subjecting the said gas to theaction of all of said rays.

3. In an apparatus for carrying out chemical reactions, in combination,a reaction chamber, means for driving gas through this chamber, meansfor producing X-rays, means for producing cathode rays, means forproducing canal rays, means for producing anode rays, all said rayproducing means being included in a common evacuated bulb, and means forsubjecting the said gas to the action of all of said rays.

4. In an apparatus for carrying out chemical reactions, in combination,a reaction chamber, means for driving gas through this chamber, anevacuated bulb, a window of sheet metal between the bulb and thereaction chamber, electrodes enclosed in said bulb and adapted toproduce -rays, cathode rays and positive rays, .all the said rays beingdirected to the metal window.

5. In an apparatus for carrying out chemical reactions, in combination,a reaction chamber, means for driving gas through this chamber, anevacuated bulb, a window consisting of a thin metal foil separating thebulb from the reaction chamber, and electrodes in said bulb including aplurality of anodes and cathodes adapted to emit X-rays, cathode raysand positive rays to-said" window.

' 6. In an apparatus for carrying out chemical reactions, incombination, a reaction chamber, means for driving gas through thischamber, an evacuated bulb, a Window consisting of a thin metal foilseparating this bulb from-the reaction chamber, cathodes and anodes inthe said bulb adapted to direct a beam of X-rays, cathode rays andpositive rays to the said window, one of said cathodes being pierced forthe passage of canal rays, and auxiliary electrodes in the said bulbadapted to accelerate the electrons striking the said window. w

7. In an apparatus for carrying out chemical reactions, in combination,a

evacuated. bulb, a window consisting of a. thin.

aoe aeo produced in a common reaction chamber} means for drivinggasthrough this chamber, an.

metal foil separating this bulb from the reaction chamber, electrodeswithin this bulb, adapted to direct a beam of cathode. rays to thev saidwindow, auxiliary electrodes adapted to accelerate the said electronsand a pierced cathode, the apertures of which, opposite the electrode insaid bulb which acts as the cooperating anode, are facing the saidwindow.

. 8. In an apparatus for carrying out chemical reactions, incombination, a reaction chamber, means for driving gas through thischamber, an evacuated bulb, a window consisting of a thin metal foilseparating this bulb from the reaction chamber, meansfor cooling thiswindow and electrodes within this bulb adapted to emit X-rays, cathoderays and positive rays to said window. I a I 9. In an apparatus forcarrying out the chemical reactions, in combination, a reaction chamber,means for driving gas through this chamber, an evacuated vessel, awindow consisting of 'a thin metal ioil'separating this vessel from thereaction chamber, means for cooling this windew and electrodes withinthis vessel adapted to emit electrons, canal rays and anode rays to thesaid window.

10. A method of. synthesizing nitrogen compounds which consists-ininfluencing nitrogen o1 atmospheric air in presence 01' water by X-rays,cathode rays and positive rays produced in a common evacuated vessel.

11. A method of synthesizing nitrogen compounds which consists ininfluencing nitrogen of atmospheric air in presence of water by X-rays,cathode rays, canal rays and anode rays evacuated bulb.

12. As an explosive gas the product obtained by influencing the nitrogenof atmospheric air in presence of water by X-rays, cathode rays andpositive rays produced in the same evacuated bulb.

13. In a fuel generator for internal combustion machines, incombination, a reaction chamber, means for driving atmospheric airthrough this chamber, means for producing X-ra'ys, means for producingcathode rays, means for producing positive rays, all said means beingenclosed in the same evacuated bulb, said bulb.

being separated from the reaction chamber by a window consisting of ametal foil.

14. Apparatus for carrying out chemical reactions consisting of anevacuated vessel, electrodes therein for the production of cathode raysand canal, rays so arranged that the rays cooperate to produce aradiation which is able to penetrate parts opaque to canal rays, andmeans outside the vessel the tube at which the radiation produced bycooperation of the cathode and canal rays emerges from the vessel.

15. Apparatus for the production of strongly active rays consisting ofan evacuated vessel,- anode and cathode arranged therein for the fordirecting a stream, of gas past the portion of production of an electroncurrent, an anode trodes therein for the production of cathode rays 75 Iand canal rays, one or said electrodes being an incandescent cathode andanother of said electrodes being a pierced cathode, a reaction chamberassociated with said evacuated vessel and means for driving gasesthrough said chamber so that said gases are subjected to the action ofsaid rays.

17. Apparatus for carrying out chemical reactions consisting of anevacuated vessel, electrodes therein for the production of negative andpositive rays, one of said electrodes being an incandescent cathode andanother of said electrodes being an anode containing a substance adaptedto produce anode rays, a reaction chamber associated with said evacuatedvessel and means for driving gases through said chamber so that saidgases are subjected to the action of said rays.

18. The method preparing an explosive gas comprising the activation ofthe nitrogen of atmospheric air in presence of water by X-rays, cathoderays and positive rays produced in the same evacuated vessel and mixingthe irradiated gas with atmospheric air.

19. A method of synthesizing nitrogen compounds which consists ininfluencing nitrogen and another substance capable of reacting therewithby X-rays, cathode rays and positive rays produced in a common bulb,said substance being one of a group consisting of H20 and H202.

20. A method of synthesizing nitrogen compounds which consists ininfluencing nitrogen of atmospheric air and another substance capable ofreacting therewith by X-grays, cathode rays and positive rays producedin a common bulb, said substance being one of a group consisting of H20and H202.

21. A method of synthesizing ammonia sulphate which consists ininfluencing nitrogen in presence or another substance by X-rays, cathoderays and positive rays produced in the same evacuated container, saidother substance bein one or a group consisting of water and hydrogenperoxide, and bringing the irradiated gas into contact with ierroussulphide and water acidifled-with sulphuric acid.

22. A method of synthesizing ammonia sulphate which consists ininfluencing nitrogen of atmospheric air in presence of another substanceby X-rays, cathode rays and positive rays produced in the same evacuatedcontainer, said other substance being one of a group consisting of waterand hydrogen peroxide and bringing the irradiated gas into contact withferrous sulphide and water acidified with sulphuric acid.

23. As an explosive gas the product obtained by influencing the nitrogenof atmospheric air in presence of another substance selected from agroup of compounds consisting of H20 and H20: by X-rays, cathode raysand positive rays produced in a common bulb.

LUDWIG HERRMANN.

